Chen Yu, Zhang Xiao, Liu Fang, He Gucheng, Zhang Ju, Houk K N, Smith Amos B, Liang Yong
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Department of Chemistry and Biochemistry, University of California, CA 90095, United States.
Chin Chem Lett. 2021 Jan;32(1):441-444. doi: 10.1016/j.cclet.2020.05.009.
Experiments indicate that a catalytic amount of CuI plays an important role in the siloxane-mediated Pd-catalyzed cross-coupling reactions with the direct use of organolithium reagents. Addition of organolithium to the siloxane transfer agent generates an organosilicon intermediate. DFT calculations indicate that CuI initially accelerates the Si-Pd(II) transmetalation of the organosilicon intermediate by the formation of CuI . Subsequently, CuI works as a shuttle between the Si-Cu(I) and Cu(I)-Pd(II) transmetalation processes.
实验表明，在直接使用有机锂试剂的硅氧烷介导的钯催化交叉偶联反应中，催化量的碘化亚铜（CuI）起着重要作用。向硅氧烷转移剂中加入有机锂会生成有机硅中间体。密度泛函理论（DFT）计算表明，CuI最初通过形成CuI促进有机硅中间体的硅-钯（II）转金属化。随后，CuI在硅-铜（I）和铜（I）-钯（II）转金属化过程之间起穿梭作用。
